Recalcitrant S(N)2 displacements at carbon C9 of quincorine and quincoridine: 1,2-Amino halides and mesylates with configurationally rigid nitrogen

Tetrahedron

Volumn 56, Issue 26, 2000, Pages 4453-4465

  Schrake, Olaf ^a   Franz, M Heiko ^a   Wartchow, R ^a   Hoffmann, H M R ^a  

^a LEIBNIZ UNIVERSITY HANNOVER   (Germany)

Author keywords

Cesium fluoride; Crown ether; Cyanide ion; Mitsunobu reaction; S(N)2 reactions

Indexed keywords

AMINOALCOHOL; QUINCORIDINE; QUINCORINE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BINDING; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONFORMATION; PRIORITY JOURNAL; STRUCTURE ANALYSIS;

EID: 0034705369     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(00)00330-6     Document Type: Article

References (26)

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18. Crystallographic data for the structure 1-OMs·HOMs reported in this paper have been deposited with the Cambridge Data Centre as supplementary publication no. CCDC-142962. Copy of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
19. All diastereotopic protons have been assigned.
20. The N,X gauche conformation is also preferred for 9-epi-bromoquinine and 9-epi-mesyloxyquinine. See Braje, W. M.; Wartchow, R.; Hoffmann, H. M. R. Angew. Chem. 1999, 38, 2540; Angew. Chem., Int. Ed. 1999, 38, 2539. Molecular mechanics calculations suggest that rotamer i (X=Cl) is favoured over (iii) by a factor of 2:1.
21. The N,X gauche conformation is also preferred for 9-epi-bromoquinine and 9-epi-mesyloxyquinine. See Braje, W. M.; Wartchow, R.; Hoffmann, H. M. R. Angew. Chem. 1999, 38, 2540; Angew. Chem., Int. Ed. 1999, 38, 2539. Molecular mechanics calculations suggest that rotamer i (X=Cl) is favoured over (iii) by a factor of 2:1.
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24. Early on, Prelog and Cerkovnikov noticed a remarkable inactivity of 2-hydroxymethyl quinuclidine towards further functionalization: "So gelang uns nicht der Austausch gegen Brom mit rauchender Bromwasserstoffsäure im Bombenrohr bei 100°C ... Die geringe Reaktionsfähigkeit dieser verhältnismäßig schwierig zugänglichen Substanzen führte zur Unterbrechung weiterer Versuche in dieser Richtung". Prelog, V.; Cerkovnikov, E. Liebigs Ann. 1940, 545, 259-260; see also Schrake, O.; Rahn, V. S.; Frackenpohl, J.; Braje, W. M.; Hoffmann, H. M. R. Org. Lett. 1999, 1, 1607.
25. Early on, Prelog and Cerkovnikov noticed a remarkable inactivity of 2-hydroxymethyl quinuclidine towards further functionalization: "So gelang uns nicht der Austausch gegen Brom mit rauchender Bromwasserstoffsäure im Bombenrohr bei 100°C ... Die geringe Reaktionsfähigkeit dieser verhältnismäßig schwierig zugänglichen Substanzen führte zur Unterbrechung weiterer Versuche in dieser Richtung". Prelog, V.; Cerkovnikov, E. Liebigs Ann. 1940, 545, 259-260; see also Schrake, O.; Rahn, V. S.; Frackenpohl, J.; Braje, W. M.; Hoffmann, H. M. R. Org. Lett. 1999, 1, 1607.
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